Copolymers of n-alkylsulfonyl- and n-arylsulfonyl-vinylamines



Patented Jul 5, i949 UNITED STATES PATENT orrica v N-AansULrom- JosephB. Dickey and'lheodore E. Stanin, ester, N. Y., assignors to EastmanKodak Com pany, Rochester, N. Y. 1 Jersey a corporation 08 New .vg.Application May it, 1948,

' Serial No. erases (erect-em ll: invtion relates to 1- andN-arylsuiionylprocess ior their me it, tion,

it is own that compounds hag oral ionic:

wherein R and Rirepresent organic radicals. can

the genconverted to the corresponding monomeric vinyl compounds byelimination of hydrogen bromide (Kharasch and Priestley, J. Amer, Chem.800., 61, 3425 (1939)); Similar sulfonyl group methyl iumte, mlitaconate, methacrylfluoridechloride, tetrafiuoroethylene, acrylic acid,

containing vimrl compounds can also be prepared ecribedand having thegeneral formula:

wherein R and R1 represent substituted or unsubstituted'alkyl and arylgroups, and X and Y represent hydrogen, halogen or cyano groups, can

.be polymerized by themselves or conjointly with other polymerizableunsaturated compounds to give resins varying in properties. For example,some of our new resinous productsare valuable for forming films, fibersand molded products.

while still others with alkyl sulphonic acid substituent groups aresurface active agents suitable for treating various textiles. Morespecifically,

R, and R1 can be methyl, ethyl, propyl, isopropyl,

n-butyl, sec.-butyl, iso-butyl, ter.-buty1 groups or these groupssubstituted by a monovalent acyl group such as sulphonlc acid or analkoxy group, such as methoxy,'or R and R1 can be phenyl,

' benzyl, ortho-, metaor para-tolyl group,'paraaminosulionylphenyl groupand other similar kind of radicals, and X and Y can be hydrogen,

inthaorylic acid, alpha -chloroacrylic acid, maleic adride, new methylsulione. prollenyl mel sulfone, ethylene malonate, vinyl tri fiuocetate,-1 r isocyanate, vinyl urethane, alpha-acetaminoacrylates, iso-butylene,butadiene, 2-chlorobutadiene, 2- acetoxy-butadiene,2-acetaminobutadiene, vinyl phthalimide, ma'leic imides, vinylacetamides and other similar kinds of compounds. It is, accordingly, anobject of our invention to provide the above defined new kind ofpolymeric compounds. A further object is to provide a process forpreparing such polymers. Other ob jects will become apparenthereinafter.

The polymerization reactions can be carried out .using any of the knownmethods, for example-by means of heat. light, or catalysts'such ashydrogen fluoride, boron trifluoride, boron trichloride, oxygen, ozone,lithium phenyl. benzoyl peroxide, furoyl peroxide. acetyl peroxide,chlorourea, dichlorodimethyl V hydantoin, and the like. In many cases,valuable and superior products can be obtained by utilizing superatmospheric pressures, for example, pressures in excess of 500atmospheres, but preferably in excess of 1000 atmospheres. Where thecompounds themselves are unable to build up the necessary pressures,

halogen such as chlorine or bromine or a cyanide.v

group. The compounds above defined can be copolymerized with one ormoreunsaturated compounds including vinyl acetate, isopropenyl acetate,methylacrylate', methyl methacrylate, vinyl methylketone, isopropenylmethyl ketone, vinyl sulfonamide, isopropenyl sulfonamide,vinylsulfonglimethylamide. malelc amide, maleic nitrile, fumaronitrile,ethyl fumarate, ethyl maleate, cisand trans-carbomethoxyacrylonitriieand amide,

an inert gas such as nitrogen or carbon dioxide is employed to obtainsuch super pressures. The polymerizationscan be eflected in mass, insolutions of inert solvents such as water, dioxane, benzene, heptane,or, polymerized in the form of beads, in emulsions, and in certaincases, in the gaseous phase. If desired, solid monomers can be meltedand sprayed concurrently into a heated chamber with any desired liquidor other solid vinyl type monomer, together with a suitable catalyst ofthe type illustrated in the preceding 7 The polymers and copolymers ofinvention ethylene propylene,

can be modifled in chemical and physical properties by hydrolysis of theside chains. For ex ample, the sulfonyl groups can be converted to aminogroups. acetyl groups to hydroxyl groups in copolymers prepared withvinyl acetate, cyasodium carbonate, tetramethyl ammonium hydroxide,trimethylbenzyl ammonium hydroxide;

hydrazine hydrate, hydrochloric acid, hydrofluoric acid, sulfuric acidor phosphoric acid. The following examples will serve to illustrate ournew polymers and the methods of obtaining the same.

Example 1.Polymer of N-methyl-N-methylsulfonyl-v'lnylamine 13.5 grams ofN-methyl-N-methylsulfonyl-- vinylamine and 0.02 gram of benzoyl peroxidewere heated together at 100 C. in a sealed tube, until polymerizationwas complete. The tube was then opened, the product granulated andpurified by extraction with alcohol. This product was a slightlyyellowish colored solid. In similar manner as above, there can beprepared polymers of N-methyl-N-methylsulfonylp -chlorovinylamine,N-methyl-N-methylsulfonyl ,8 -bromovinylamine orN-methyl-N-methylsulfonyl ,6 cyanovinylamine.

Example 2.Plymer of N-methz l-N-methylsulfcmyl-isopropenylamine 1. Theproduct was a slightly yellowish colored solid.

Example 3.-C0polvmer of N-phenyl-N -phenylsuljonyl-vinylamine andN-methpl-N-paratolylsulfonyl-p-chlorovinylamine grams ofN-phenyl-lt-phenylsulfonyl-vinylamine, 10 grams ofN-methyl-N-para-tolylsul fonyl-p-chlorovinylamine and 0.2 gram ofbenzoyl peroxide were dissolved in formamide and heated at 50 0., untilno further change could be noted. Water was then added and the yellowishcolored product filtered oil, washed with water and dried. In place offormamide, there can be substituted acetic acid.

Example 4.--Polymer of sodium salt of N-sulfoethyl-N-ethylsul/onylisopropenylamine there can be substituted in the above example,

' 20 grams of the sodium salt of N-sulfoethyl-N-ethylsulfonyl-isopropenylamine and 50 cc. of water were charged into anautoclave and heated to 180-220 C. under a pressure of about 3000atmospheres maintained by means of nitrogen gas. After 15 hours, theautoclave was cooled and the viscous mass removed. The product waswatersoluble and useful as a surface active agent for the treatment ofvarious textiles.

Example 5.--tLopol1nner o N-methyl-N-phenylsulfonyl-vinylamine and vinylacetate product was purified by dissolving in acetone and pouring intowater. In place of vinyl acetate,

vinyl trifluoroacetate, vinyl butyrate, isopropenyl acetate, orcyclohexenyl acetate.

Example 6.Copolymer of N-ethul-N-para-auljonylphenylsuljamlneisopropenylamine and styrene 20 grams of styrene and 1 gram ofN-ethyl-N- para-sulfonylphenylsulfamine-isopropenylamine werepolymerized, in the presence of 0.05 gram of benzoyl peroxide at C.,until no further change could be observed. The nearly glass-clearpolymer was moldable as obtained. The molecular proportions of the aboveconstituents can be varied within wide limits, since usable polymericproducts are obtained with starting compositions, wherein styrene can bepresent in about from 1 to 99 parts in a. total mixture of 100 parts. Inplace of styrene in the above example, there can be substitutedalpha-methyl styrene, 2,4-dichlorostyrene, alpha-acetoxystyrene,ortho-acetamino styrene, para-sulfonamido styrene to obtain relatedpolymeric, moldable products.

Example 7.Copolymer of N-methyl-N-methylsulfonyl-m'nz/lamine and methylmethacrulate 10 grams of N-methyl-N-methylsulfonyl-vinylamine, 30 gramsof methyl methacrylate and 0.50 gram of benzoyl peroxide werepolymerized to completion at 60 C. The product was obtained as aslightly yellowish-white, moldable solid. In place of the methylmethacrylate in the above example, there can be substituted anequivalent amount of methyl acrylate, butyl acrylate,alphachloroethylacrylate, cisand trans-,B-cyanomethylacrylate to obtainrelated resinous products. The properties of the resulting products canbe varied by changing the proportion of the monomeric compounds of thestarting materials. Thus, useful products can be obtained bypolymerizing mixtures wherein the alkylsulionyl- 'vinylamine varies fromabout 1 to 99 molecular parts and the acrylate from about 99 to 1molecular parts.

Example 8.C' polymer of N-methyl-N methylsulfonyl-ismopenylamine andunsaturated alkyl esters Example 9.Copolz)mer ofN-phenyl-N-butylsulfonyl-vinylamine and methyl isopropeny ketone 5 gramsof N-phenyl-N-butylsulfonyl-vinylamine, 20 grams of methyl isopropenylketone' and 0.30 gram of benzoyl peroxide were polymerized at 70 C. rThe resulting solid was purified by dissolving 'in acetone andprecipitating in water. In place of the methyl isopropenyl ketone. therecan be substituted in the above example, an equivalent amount of methylvinyl ketone, methyl vinyl sulfone or methylisopropenylsulfone to obtainrelatedpolymeric products.

Example lit-Commuter of N-methyl-N-crthorylonitrile grams ofN-methyl-N-ortho-tolylsulionyialpha-chloro-vinylamine and grams ofacryperoxide as a catalyst. The yellowish-white solid was acetonesoluble. For the acrylonitrile in the above example, there can besubstituted alphatolylsul/onyl-alpha-chlorovinyiamtne and aev lonitrilewere polymerized at 50 0., using benzoyl methacrylonitrile oralpha-acetoxy-acrylonitrile.

Example 11.Copol1lmer of N-methyl-Mphenylsulfonyl-vinylamine and acrylicamide Example 12.-Copolumer of N-methyl-N-methyl--suljonyl-isopropenylamine and ethylene 5 grams ofN-methyl-N-methyisulionyl-isop1 openylamine were charged intoanautoclave, 2

7 grams of ethylene added and the mixture slowly heated to 180 0., undera nitrogen gas pressure of about 300' atmospheres, until polymerizationwas complete. The hard, tough polymerobtained thereby was suitable forforming films, fibers and for molding Pu poses. In place of ethylene inthe above example, there can be substituted propylene or isobutylene.The polymerizations can be carried out using any desired ratio of thealkyisuli'onyl-vinylamine to the unsaturated hydrocarbon. Also more thantwo compounds capable of polymerizing can be used, for example, aresinous solid is obtained with 5 grams of N-benzyi-N- paratolylsulfonyl alpha phenylvinylamine, 5 grams of ethylene and 5 grams ofisopropenyl acetate polymerized in the manner above described.

Example 13.Copolymer of N-p acetoethyl-N- phenylsulfonyl a l p h aethylvinylamine and vinyl chloride 10 grams ofN-fi-acetoethyl-N-phenylsulionylalpha-ethylvinylamine, 5 grams of vinylchloride and 0.10 gram of benzoyl peroxide were polymerized at 50, C.,in a sealed tube, until no further change took place. "I'he slightlyyellowish polymer so obtained was tough and moldable. For

the vinyl chloride in the above example, there can be substitutedisopropenyl chloride, alpha-chlorostyrene, fl-chloroallyl acetate,vinylidene dichloride, vinylidene chloride-fluoride ortetrachloroethylene to obtain similar kind of halogen containingcopolymers.

Example 14.-Oopolymer of N-ethyl-N-phenylsulfonyl-vinylamine andtetrachloroe tlwlene 5 grams 0! N-ethyl-N-phenylsulionyl-vinylamine and5 grams of tetrachloroethylene were polymerized in an autoclave at atemperature ofabout 200 C., under a pressure of about 2000 at- Q Qll'mmple 15. C'opolumer of N-methyl-N-plieiwlsultoiwl b e t aeyancvinylamine and butaatene tained was a tough. elastic and.vulcanizable solid. In place of the butadiene in the above example,there can be substituted 2-methylbutadiene. 2,3-dimethylbutadiene,l-cyanobutadiene, 2-cyanobutadiene, i-acyloxybutadiene, 2-acyloxybutadiene or z-chlorobutadiene to obtain related polymeric products.

' What we claim is:

1. A copolymer obtained by heating in the presence of a polymerizationcatalyst a mixture containing as the sole unsaturated components from 5to 95 molecular parts oiN-methyl-N-phenylsulionyl-vinylamine and from 95to 5 molecular parts of vinyl acetate.

2. A copolymer obtained by heating in the presence 01' a polymerizationcatalyst a mixture containing as the sole unsaturated components from 5to 95 molecular parts of N-methyl-N-methylsulionyl-vinylamine and from95 to 5 molecular parts of methyl methacrylate.

3. The process which comprises heating in the presence oi apolymerization catalyst a mixture containing as the sole unsaturatedcomponents from 5 to 95 molecular parts of N-methyl-N-phenylsuli'onyl-vlnylamine and from 95 to 5 molecular parts of vinylacetate.

4. The process which comprises heating in the I presence oi apolymerization catalyst a mixture containing as the sole unsaturatedcomponents mospheres maintained by injection of nitrogen.

The product was a tough. h melting solid.

irom 5 to molecular parts of N-methyl-N- methylsulionyl-vinylamine andfrom 95 to 5 molecular parts of methyl methacrylate.

5. A copolymer obtained by heating in the presence of a polymerizationcatalyst a mixture containing as the sole unsaturated components i'rom'5 to as molecular parts of a cbmpound having the general formula:

1?. cHFQH-is-sm-R.

wherein R and. R1 each represents a member selected from the groupconsisting of an alkyl group having from 1 to 4 carbon atoms and aphenyl group, and from 95 to 5 molecular parts of a compound containinga polymerizable containing as the sole unsaturated components 2 from 5to 95 molecular parts of a compound havj ing the general formula:

wherein R and R1 each represents a member selected irom the groupconsisting of an alkyl group oiirom 1 to 4 carbon atoms and a phenylgroup,

3,476,484 I 1 1 8 and from 06 to Imam-pub of u comma REFERENCE! crr FThe following references are or record in th A me of this pat-ant: 7

mlmtnl. a v tmrrm sums PATENTS JOSEPH B. DICKIY. 7 Number Name Date 73,317,804 Reppo Apr. 27, 1948 TEIODORI I. B'IANIM

